Correlative operando and cryo-techniques for visualising structure and chemistry in liquid-solid nanoscale systems

Session

Multiscale and Correlative Microscopy Approaches to Microanalysis and Spectroscopy

Authors

Neil Mulcahy (1), Prof. Mary P. Ryan (1), Dr. Shelly Conroy (1)

Affiliations

1. Imperial College London

Abstract text

Materials that are critical for future advancements in technologies for the energy transition, such as new batteries or materials for the hydrogen economy and catalysis for new fuels, often contain highly complex interfaces that are difficult to characterise using single conventional techniques. These systems typically contain solid-liquid or liquid-liquid interfaces involving low atomic weight, mobile and/or labile elements such as hydrogen, carbon, and lithium, which are the most challenging to quantitatively characterise in their state of interest [1]. Too often different experimental microscopy and spectroscopy techniques are carried out in isolation with no clear way to combine and quantify multiple data streams originating from different techniques. Having a precise understanding of the composition and structure of these systems in their states of interest at the atomic scale using multiple techniques will lead to understanding how these materials perform during service and what controls their behaviour and/or limits their lifetime. 

This project aims to develop a truly correlative operando and cryogenic microscopy approach involving cryogenic atom probe tomography (APT), cryogenic transmission electron microscopy (TEM), liquid cell transmission electron microscopy (LCTEM) and nanoscale synchrotron based spectro-microscopy (in partnership with Diamond Light Source) to image such systems. This involves developing protocols, tools, and analytical methods using model systems to build the capability to fully represent energy-relevant reactive systems. 

The first challenge is to understand and mitigate the migration and damage of species during preparation, transfer, and characterisation, particularly when attempting to maintain the specimens in an environment close to that faced in operando. This will be completed using already established sample preparation workflows for LCTEM [2]. While cryogenic APT and TEM sample preparation workflows will be combined using a cryogenic plasma focused ion beam (PFIB), FerroVac Vacuum Cryo Transfer Module, and an inert atmosphere glovebox with cryo transfer capabilities. This will allow for cryogenic TEM-APT compatible samples to be transferred under cryogenic conditions between different instruments in their state of interest [3][4].

The second challenge is to collect information not only on structure but also activity in-situ, composition, and chemical state. This in many cases also needs to be completed on the same specimen using different techniques and correlating these results. LCTEM offers unprecedented spatial and temporal resolution for visualising liquid phase processes at the nanoscale such as battery solid–electrolyte interface (SEI) formation. LCTEM not only preserves the liquid state of the specimens inside the TEM vacuum, but also allows the in-situ observation of the processes at the nanoscale [5]. Cryogenic electron microscopy allows analysis of frozen liquids, frozen liquid/solid interfaces and light, mobile elements such as hydrogen and lithium captured in their state of interest [1]. Cryogenic APT is a high-resolution microscopy technique that provides sub nm spatial resolution and ppm compositional information, ideal for observing nanoscale features where localised compositional variation can be expected [6]. X-ray studies offer complementary capabilities to analyse additional properties of the system such as high-energy resolution spectroscopy for local bonding and chemical information [7]. 

A third challenge is the need to establish a protocol to converge the data streams originating from the various microscopy and microanalysis techniques used. These challenges are critical to overcome in order to realise a fully cryo-enabled multi-microscopy characterisation approach. 

In this presentation, we will discuss these challenges and progress in developing a truly correlative approach to characterising sensitive materials and interfaces.

References

[1] - X. Wang, Y. Li, Y.S. Meng, Cryogenic Electron Microscopy for Characterizing and Diagnosing Batteries, Joule, Volume 2, Issue 11, (2018).

[2] - Chee, S.W., Tan, S.F., Baraissov, Z. et al. Direct observation of the nanoscale Kirkendall effect during galvanic replacement reactions. Nat Commun 8, 1224 (2017).

[3] - Cryogenic Focused Ion Beam Enables Atomic-Resolution Imaging of Local Structures in Highly Sensitive Bulk Crystals and Devices, Cryst. Growth Des., 21, 2, 1314–1322, (2021).

[4] - Stephenson LT, Szczepaniak A, Mouton I, Rusitzka KAK, Breen AJ, Tezins U, et al. The Laplace Project: An integrated suite for preparing and transferring atom probe samples undercryogenic and UHV conditions. PLoS ONE 13(12): e0209211, (2018).

[5] - Tan, S. F., Raj, S., Bisht, G., Annadata, H. V., Nijhuis, C. A., Král, P., Mirsaidov, U., "Nanoparticle interactions guided by shape-dependent hydrophobic forces." Advanced materials Adv. Mater. 2018, 30, 1707077, (2018).

[6] - J. W. Valley, D. A. Reinhard, A. J. Cavosie, T. Ushikubo, D. F. Lawrence, D. J. Larson, T. F. Kelly, D. R. Snoeyenbos, A. Strickland; Nano- and micro-geochronology in Hadean and Archean zircons by atom-probe tomography and SIMS: New tools for old minerals. American Mineralogist, 100 (7): 1355–1377, (2015).

[7] - About Us, Diamond light source, accessed on 08/02/2023 { https://www.diamond.ac.uk/Home/About.html}